Fiber coating composition having an invisible marker and process for making same

• US 6,217,794 B1
• Filed: 04/30/1999
• Issued: 04/17/2001
• Est. Priority Date: 06/01/1998
• Status: Expired due to Fees

• Current Assignee: Authentix, Inc.
• Original Assignee: Isotag Technology, Inc. (Authentix, Inc.)
• Inventors: Neal, Richard Dixon, Krutak, James John Sr., Jackson, Barbara Crawford
• Primary Examiner(s): KOSLOW, CAROL M
• Application Number:
  US09/302,382
• Time in Patent Office: 718 Days
• Field of Search: 106/31.15, 252/301.16, 252/301.34, 252/301.35, 864/8, 427/157, 428/670
• US Class Current: 252/301.35
• CPC Class Codes: C08K 5/0091 Complexes with metal-heteroatom-bonds
• CPC Class Codes: D06P 1/0012 Effecting dyeing to obtain luminescent or phosphorescent dyeings
• CPC Class Codes: D06P 1/14 using phthalocyanine dyes without vatting D06P1/38, D06P1/40 take precedence
• CPC Class Codes: D21H 21/30 Luminescent or fluorescent substances, e.g. for optical bleaching D21H21/40 takes precedence
• CPC Class Codes: Y10T 428/12875 Platinum group metal-base component

Abstract

Fibers having at least one near-infrared fluorescing compound associated therewith are prepared by contacting the fibers with the fluorescing compound(s) dissolved in an organic solvent. Suitable organic solvents include ketones and alcohols. The fibers may subsequently be air-dried to remove any remaining volatiles. Fibers coated with the marker solution desirably have less than 1 weight percent of the marker coated thereon.

Claims

1. A composition comprising a fiber and a near-infrared fluorescing compound associated with said fiber, wherein said near-infrared fluorescing compound comprises a solution having about 0.5 weight percent of a near-infrared fluorophore dissolved in an organic solvent.

2. The composition of claim 1 wherein said fiber is selected from the group comprising polyester fibers, polyolefin fibers, polyphenylene sulfide fibers, modacrylic fibers, nylon fibers, viscose rayon fibers, cotton fibers, wool fibers, wood pulp and blends thereof.

3. The composition of claim 1 wherein said organic solvent is selected from the group consisting of ketones and alcohols.

4. The composition of claim 3 wherein said organic solvent is acetone.

5. The composition of claim 1 wherein said solution has from about 10 ppm to about 25 ppm of said near-infrared fluorophore in an organic solvent.

6. The composition of claim 1 wherein said near infrared fluorescent compound is selected from the group consisting of phthalocyanines, 2,3-naphthalocyanines and squaraines corresponding to Formulae I, II and III:

where Pc and Nc represent the phthalocyanine and naphthalocyanine moieties of Formulae Ia and IIa,

respectively, covalently bonded to a moiety selected from the group consisting of hydrogen and metals selected from the group consisting of AlCl, AlBr, AlOH, AlOR₅, AlSR₅, Ge, Ge(OR₆), Ga, InCl, Mg, SiCl₂, SiF₂, SnCl₂, Sn(OR₆)₂, Si(SR₆)₂, or Zn, wherein R₅ and R₆ are selected from the group consisting of hydrogen, alkyl, aryl, heteroaryl, lower alkanoyl, trifluoroacetyl, groups of the formulae;

R₇, R₈, and R₉ are independently selected from the group consisting of alkyl, phenyl or phenyl substituted with lower alkyl, lower alkoxy and halogen;

X is selected from the group consisting of oxygen, sulfur, selenium, tellurium and a group of the formula N(R₁₀), wherein R₁₀ is selected from the group consisting of hydrogen, cycloalkyl, alkyl, acyl, alkylsufonyl, and aryl or R₁₀ and R taken together form an aliphatic or aromatic ring with the nitrogen atom to which they are attached;

Y is selected from alkyl, aryl, heteroayl, halogen or hydrogen;

R is selected from the group consisting of unsubstituted or substituted alkyl, alkenyl, alkynyl, C₃-C₈ cycloalkyl, aryl, heteroaryl, and groups of the formulae

or (X—

R) moiety is selected from the group consisting of alkylsulfonylamino,

 

arylsulfonylamino, or a group selected from the formulae —

X(C₂H₄O)^zR¹,

wherein R¹ is hydrogen or R is as defined above;

z is an integer from 1 to 4;

or two (X—

R) moieties can be taken together to form divalent substituents of the formula;

 

wherein each X₁ is independently selected from the group consisting of —

O—

, —

S—

, and —

N(R₁₀)— and

A is selected from the group consisting of ethylene;

propylene;

trimethylene; and

such groups substituted with C₁-C₄ alky, C₁-C₄ alkoxy, aryl and cycloalkyl;

1,2-phenylene and 1,2-phenylene containing 1-3 substituents selected from the group consisting of C₁-C₄ alkyl, C₁-C₄ alkoxy and halogen;

R₁ and R₂ are independently selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, halogen, aryloxy, lower alkyl-thio, arylthio, lower alkylsulfonyl;

arylsulfonyl;

lower alkyl-sulfonyl-amino, lower alkanoylamine, arylsulfonylamino, cycloalkyl-sulfonylamino, carboxy, unsubstituted and substituted carbamoyl and sulfamoyl, lower alkoxycarbonyl, hydroxy, lower alkanoyloxy, and groups of the formulae;

R₃ and R₄ moieties are independently selected from the group consisting of hydrogen, lower alkyl, alkenyl and aryl;

n is an integer from 0-16;

n₁ is an integer from 0-24, provided the sums of n+m and n₁+m₁ are 16 and 24, respectively.

7. A composition comprising a fiber selected from the group consisting of polyester fibers, polyolefin fibers, polyphenylene sulfide fibers, modacrylic fibers, nylon fibers, viscose rayon fibers, cotton fibers, wool fibers, wood pulp and blends thereof and a near-infrared fluorescing compound selected from the group consisting of phthalocyanines, 2,3-naphthalocyanines and squaraines corresponding to Formulae I, II and III:

where Pc and Nc represent the phthalocyanine and naphthalocyanine moieties of Formulae Ia and IIa,

respectively, covalently bonded to a moiety selected from the group consisting of hydrogen and metals selected from the group consisting of AlCl, AlBr, AlOH, AlOR₅, AlSR₅, Ge, Ge(OR₆), Ga, InCl, Mg, SiCl₂, SiF₂, SnCl₂, Sn(OR₆)₂, Si(SR₆)₂, or Zn, wherein R₅ and R₆ are selected from the group consisting of hydrogen, alkyl, aryl, heteroaryl, lower alkanoyl, trifluoroacetyl, groups of the formulae;

R₇, R₈, and R₉ are independently selected from the group consisting of alky, phenyl or phenyl substituted with lower alkyl, lower alkoxy and halogen;

X is selected from the group consisting of oxygen, sulfur, selenium, tellurium and a group of the formula N(R₁₀), wherein R₁₀ is selected from the group consisting of hydrogen, cycloalkyl, alkyl, acyl, alklsulfonyl, and aryl or R₁₀ and R taken together form an aliphatic or aromatic ring with the nitrogen atom to which they are attached;

Y is selected from alkyl, aryl, heteroaryl, halogen or hydrogen;

R is selected from the soup consisting of unsubstituted or substituted alkyl, alkenyl, alkynyl, C₃-C₈ cycloalkyl, aryl, heteroaryl, and groups of the formulae

or (X—

R) moiety is selected from the group consisting of alkylsulfonylamino,

 

arylsulfonylamino, or a group selected from the formulae —

X(C₂H₄O)_zR¹,

wherein R¹ is hydrogen or R is as defined above;

z is an integer from 1 to 4;

or two (X—

R) moieties can be taken together to form divalent substituents of the formula;

 

wherein each X₁ is independently selected from the group consisting of —

O—

,—

S—

, and —

N(R₁₀)— and

A is selected from the group consisting of ethylene;

propylene;

trimethylene; and

such groups substituted with C₁-C₄ alkyl, C₁-₄ alkoxy, aryl and cycloalkyl;

1,2-phenylene and 1,2-phenylene containing 1-3 substituents selected from the group consisting of C₁-C₄ alkyl, C₁-C₄ alkoxy and halogen;

R₁ and R₂ are independently selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, halogen, aryloxy, lower alkyl-thio, arylthio, lower alkylsulfonyl;

arylsulfonyl;

lower alkyl-sulfonyl-amino, lower alkanoylamine, arylsulfonylamino, cycloalkyl-sulfonylamino, carboxy, unsubstituted and substituted carbamoyl and sulfamoyl, lower alkoxycarbonyl, hydroxy, lower alkanoyloxy, and groups of the formulae

 

R₃ and R₄ moieties are independently selected from the group consisting of hydrogen, lower alkyl, alkenyl and aryl;

n is an integer from 0-16;

n₁ is an integer from 0-24, provided the sums of n+m and n₁+m₁ are 16 and 24, respectively

associated with said fiber,

wherein said near-infrared fluorescing compound comprises a solution having about 0.5 weight percent of a near-infrare fluorophore dissolved in an organic solvent selected from the group consisting of ketones and alcohols.

8. A method for tagging fibers with a near-infrared compound comprising the step of contacting said fibers with a solution having in the range of 10 ppm to 0.5 wt % of said near-infrared fluorescing compound dissolved in an organic solvent so as to coat the fibers with in the range of from about 0.1 to about 3 weight percent of said solution.

9. The method of claim 8 wherein said fibers are selected from the group consisting of natural fibers and synthetic fibers.

10. The method of claim 9 wherein said synthetic fibers are selected from the group consisting of polyester, polyolefin, polyhenylene sulfide, polyacrylic, nylon, viscose rayon and blends thereof.

11. The method of claim 8 wherein said near-infrared fluorescing compound selected from the group consisting of phthalocyanmes, 2,3-naphthalocyanines and squaraines corresponding to Formulae I, II and III:

where Pc and Nc represent the phthalocyanine and naphthalocyanine moieties of Formulae Ia and IIa,

respectively, covalently bonded to a moiety selected from the group consisting of hydrogen and metals selected from the group consisting of AlCl, AlBr, AlOH, AlOR₅, AlSR₅, Ge, Ge(OR₆), Ga, InCl, Mg, SiCl₂, SiF₂, SnCl₂, Sn(OR₆)₂, Si(SR₆)₂, or Zn, wherein R₅ and R₆ are selected from the group consisting of hydrogen, alkyl, aryl, heteroaryl, lower alkanoyl, trifluoroacetyl, groups of the formulae;

R₇, R₈, and R₉ are independently selected from the group consisting of alkyl, phenyl or phenyl substituted with lower alkyl, lower alkoxy and halogen;

X is selected from the group consisting of oxygen, sulfur, selenium, tellurium and a group of the formula N(R₁₀), wherein R₁₀ is selected from the group consisting of hydrogen, cycloalkyl, alkyl, acyl, alkylsulfonyl, and aryl or R₁₀ and R taken together form an aliphatic or aromatic ring with the nitrogen atom to which they are attached;

Y is selected from alkyl, aryl, heteroaryl, halogen or hydrogen;

R is selected from the group consisting of unsubstituted or substituted alkyl, alkenyl, alkynyl, C₃-C₈ cycloalkyl, aryl, heteroaryl, and groups of the formulae

or (X—

R) moiety is selected from the group consisting of alkylsulfonylamino,

 

arylsulfonylamino, or a group selected from the formulae —

X(C₂H₄O)_zR¹,

wherein R¹ is hydrogen or R is as defined above;

z is an integer from 1 to 4;

or two (X—

R) moieties can be taken together to form divalent substituents of the formula;

 

wherein each X₁ is independently selected from the group consisting of —

O—

, —

S—

, and —

N(R₁₀)— and

A is selected from the group consisting of ethylene;

propylene;

trimethylene; and

such groups substituted with C₁-C₄ alkyl, C₁-C₄ alkoxy, aryl and cycloalkyl;

1,2-phenylene and 1,2-phenylene containing 1-3 substituents selected from the group consisting of C₁-C₄ alkyl, C₁-C₄ alkoxy and halogen;

R₁ and R₂ are independently selected from the group consisting of hydrogen, lower alkyl, lower alkoxy, halogen, aryloxy, lower alkyl-thio, arylthio, lower alkylsulfonyl;

arylsulfonyl;

lower alkyl-sulfonyl-amino, lower alkanoylamine, arylsulfonylamino, cycloalkyl-sulfonylamino, carboxy, unsubstituted and substituted carbamoyl and sulfamoyl, lower alkoxycarbonyl, hydroxy, lower alkanoyloxy, and groups of the formulae,

 

R₃ and R₄ moieties are independently selected from the group consisting of hydrogen, lower alkyl, alkenyl and aryl;

n is an integer from 0-16;

n₁ is an integer from 0-24, provided the sums of n+m and n₁+m₁ are 16 and 24, respectively.

12. A method for tagging fibers with a near-infrared compound comprising the step of contacting said fibers with a solution having in the range of 10 ppm to 0.5 wt % of said near-infrared fluorescing compound dissolved in an organic solvent, wherein said natural fibers are selected from the group consisting of wool, cotton, flax, jute, paper, fur, cardboard, wood pulp and mixtures thereof.